CN104218143B - A kind of preparation method of BiAgSeTe base thermoelectricity materials - Google Patents
A kind of preparation method of BiAgSeTe base thermoelectricity materials Download PDFInfo
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Abstract
The present invention is a kind of preparation method of BiAgSeTe base thermoelectricity materials, the material component prepares BiAgSeTe base high-performance thermoelectric block body materials with Bi, Ag, Se and Te simple substance powder that purity is 99.99% as raw material with low temperature melting technology combination discharge plasma sintering.The present invention program simple, fast can prepare BiAgSeTe base block thermoelectric materials, by the thermoelectric (al) power factor that material can be significantly improved with when technological parameter for optimizing element in this material, substantially on the basis of not increasing the thermal conductivity of material, the advantages of improve the thermoelectricity capability of material.BiAgSeTe sills are a kind of very potential thermo-electric converting materials.
Description
Technical field
The present invention is a kind of preparation method of BiAgSeTe base thermoelectricity materials, belongs to technical field of energy material.
Background technology
With the pursuit of the environmentally friendly regenerative resource of the mankind, semiconductor generates electricity and refrigeration application research will make thermoelectricity
Transition material micro element produces profound significance to entire society's resources conservation and environmental protection, meets human kind sustainable development war
Slightly.Either thermoelectric power generation, or thermoelectric cooling application, all be unable to do without generating high and refrigerating efficiency, determine its efficiency
Key factor be the thermoelectricity capability of material just.The performance of thermoelectric material typically represents (ZT by dimensionless thermoelectric figure of merit ZT
=α2σ T/ κ, wherein α, σ, κ, T represent Seebeck coefficients, electrical conductivity, thermal conductivity and the absolute temperature of material, wherein α respectively2σ
It is the power factor in thermoelectricity capability).Therefore good thermoelectric material should have Seebeck coefficients and low resistivity high,
Low thermal conductivity and power factor high.At present, improve the mode of conducting material thermoelectricity performance and mainly have doping vario-property, into sub-control
System, institutional framework control etc., in the case where material power factor is improved, do not increase thermal conductivity, so as to improve material relatively
Thermoelectricity capability.It is also current thermoelectric material research emphasis to develop new multicomponent thermoelectric material and technique synthesis simultaneously.
The content of the invention
The technical scheme is that in research Bi-Te binary compounds Bi2Te3And its spread out on the basis of doping vario-property compound
Raw multi-element compounds are used as proposition during thermoelectric material, there is provided a kind of preparation side of BiAgSeTe base thermoelectricity materials
Method, BiAgSeTe base thermoelectricity materials have no domestic and international relevant report, and the cubic structure of BiAgSeTe base thermoelectricity materials determines it
With relatively low thermal conductivity, its electric property relative mistake is a little, can effectively be adjusted by adjusting different Se and Te atom ratios
The carrier concentration of the material, improves its electricity transmission performance, is beneficial to improve its thermoelectricity capability.In addition, by the material
Expect the control of synthesis technique, the performance to optimizing material also functions to very important effect.In BiAgSeTe base thermoelectricity materials, by
In the low reason of the fusing point of Bi, Se and Te metal, the second phase is easily generated in building-up process, increase brilliant dielectric resistance, be unfavorable for this material
The thermoelectricity capability of material system is improved, and technical solution of the present invention mainly makes the units such as low-melting-point metal Bi, Se and Te using process annealing
It is plain solid molten, strict regulation control Se, Te atomic ratio, then by low temperature melting combination discharge plasma sintering, in optimization material
While the thermoelectric (al) power factor, thermal conductivity is not increased relatively, the effect of the material system thermoelectricity capability is improved so as to reach.
The purpose of the present invention is achieved through the following technical solutions：
Technical solution of the present invention proposes a kind of BiAgSeTe base thermoelectricity materials, and its feature exists：The chemical general formula of the material
For：BiAgSe1-xTe1+x, the span of x is -0.05~0.05.
Technical solution of the present invention also proposed a kind of method for preparing the BiAgSeTe base thermoelectricity materials, and its feature exists
In：With Bi, Ag, Se and Te simple substance powder that purity is 99.99% as raw material, weighed by the proportioning of chemical general formula, ground with agate
Alms bowl is well mixed raw material, is pressed into block and is put into vacuum drying chamber, and drying temperature is 200 DEG C, and process time is 48h, so
Afterwards by block Chan it is broken after be put into stainless steel jar mill, add absolute ethyl alcohol wet-milling 12 hours under 400rpm, absolute ethyl alcohol plus
It is 5~10 times of block volume to enter amount, then the powder of milled is put into 60 DEG C of vacuum bellows and is dried 24 hours, dried
Powder is put into graphite jig, by discharge plasma sintering into block materials, in sintering process, programming rate be 80 DEG C~
150 DEG C/min, sintering temperature is 450 DEG C, and pressure is 30Mpa~60Mpa, soaking time 3~6 minutes, you can obtained
BiAgSeTe base thermoelectricity materials.
When weighing raw material by the proportioning of chemical general formula, the value of x is 0,0.002,0.004,0.008,0.01,0.02,
0.03rd, 0.04 or 0.05.
It is an advantage of the invention that：Technical solution of the present invention can be accurate, succinct a kind of different Se, Te atoms of preparing match somebody with somebody
The BiAgSeTe base block thermoelectric materials of ratio.Solve in thermoelectricity capability optimization process, electric property becomes with heat conveyance performance parameter
The paradox of change, the overall thermoelectricity capability for improving material.By low temperature melting, the proportioning content of precise control each element makes
Obtaining can adjust Se, Te atomic ratio in synthesizing block material during discharge plasma sintering, regulate and control carrier concentration,
The relative power factor for not increasing thermal conductivity, improving BiAgSeTe sills on the basis of raising electric property.
Brief description of the drawings
Fig. 1 is the XRD of the BiAgSeTe base thermoelectricity material blocks of technique synthesis in embodiment 1；
Fig. 2 is the SEM of the BiAgSeTe base thermoelectricity material blocks of technique synthesis in embodiment 1；
Specific embodiment
Technical solution of the present invention is made below with reference to embodiment further say detailed description：
With Bi, Ag, Se and Te simple substance powder that purity is 99.99% as raw material, by chemical general formula BiAgSe1-xTe1+x(x
Span for -0.05~proportioning 0.05) weighs, as shown in table 1.
The BiAgSeTe base thermoelectricity materials raw material components of table 1 and proportioning
Each numeric item represents the implementation of a BiAgSeTe base block thermoelectric material raw material components and proportioning in table 1
Example.
The preparation process of BiAgSeTe base thermoelectricity materials is as follows：
Grinding alms bowl with agate is well mixed raw material, is pressed into block and is put into vacuum drying chamber, and drying temperature is 200 DEG C,
Process time is 48h, then by block Chan it is broken after be put into stainless steel jar mill, add absolute ethyl alcohol wet-milling 12 under 400rpm small
When, the addition of absolute ethyl alcohol is 5~10 times of block volume, then the powder of milled is put into 60 DEG C of vacuum bellows and is dried
24 hours, dried powder was put into graphite jig, by discharge plasma sintering into block materials, in sintering process, was risen
Warm speed be 80 DEG C~150 DEG C/min, sintering temperature be 450 DEG C, pressure be 30Mpa~60Mpa, soaking time 3~6 minutes,
BiAgSeTe base thermoelectricity materials can be obtained.
In table 1 each embodiment be prepared into BiAgSeTe base thermoelectricity materials some processes parameter it is as follows：
Embodiment 1
The addition of absolute ethyl alcohol is 5 times of block volume, dries powder by during discharge plasma sintering, heating up
Speed is 80 DEG C/min, and pressure is 40Mpa, and soaking time 6 minutes, that is, the molecular formula for obtaining is BiAgSeTe thermoelectric block body materials
Material, in 723K, power factor is 445 μ Wm‐1K‐2, thermal conductivity is 0.72Wm‐1K‐1.Fig. 1 is technique synthesis in embodiment 1
The XRD of BiAgSeTe base thermoelectricity material blocks；Fig. 2 is the BiAgSeTe base thermoelectricity material blocks of technique synthesis in embodiment 1
SEM；
Embodiment 2：The addition of absolute ethyl alcohol is 6 times of block volume, dry powder by discharge plasma sintering into
Block materials, programming rate is 100 DEG C/min, and pressure is 50Mpa, soaking time 5 minutes, you can obtaining molecular formula is
BiAgSe0.998Te1.002Thermoelectric block body material.By test performance, its power factor in 723K is 457 μ Wm-1K-2, thermal conductivity
Rate is 0.74Wm-1K-1。
Embodiment 3：The addition of absolute ethyl alcohol is 6 times of block volume, dry powder by discharge plasma sintering into
Block materials, programming rate is 120 DEG C/min, and pressure is 60Mpa, soaking time 4 minutes, you can obtaining molecular formula is
BiAgSe0.996Te1.004Thermoelectric block body material.By test performance, its power factor in 723K is 474 μ Wm-1K-2, thermal conductivity
Rate is 0.81Wm-1K-1。
Embodiment 4：The addition of absolute ethyl alcohol is 6 times of block volume, dry powder by discharge plasma sintering into
Block materials, programming rate is 150 DEG C/min, and pressure is 50Mpa, soaking time 3 minutes, you can obtaining molecular formula is
BiAgSe0.994Te1.006Thermoelectric block body material.By test performance, its power factor in 723K is 488 μ Wm‐1K‐2, thermal conductivity
Rate is 0.82Wm‐1K‐1。
Embodiment 5：The addition of absolute ethyl alcohol is 6 times of block volume, dry powder by discharge plasma sintering into
Block materials, programming rate is 150 DEG C/min, and pressure is 60Mpa, soaking time 3 minutes, you can obtaining molecular formula is
BiAgSe0.992Te1.008Thermoelectric block body material.By test performance, its power factor in 723K is 491 μ Wm‐1K‐2, thermal conductivity
Rate is 0.84Wm‐1K‐1。
Embodiment 6：The addition of absolute ethyl alcohol is 10 times of block volume, dry powder by discharge plasma sintering into
Block materials, programming rate is 150 DEG C/min, and pressure is 50Mpa, soaking time 5 minutes, you can obtaining molecular formula is
BiAgSe0.99Te1.01Thermoelectric block body material.By test performance, its power factor in 723K is 529 μ Wm‐1K‐2, thermal conductivity
Rate is 0.90Wm‐1K‐1。
Embodiment 7：The addition of absolute ethyl alcohol is 10 times of block volume, dry powder by discharge plasma sintering into
Block materials, programming rate is 150 DEG C/min, and pressure is 50Mpa, soaking time 6 minutes, you can obtaining molecular formula is
BiAgSe0.98Te1.02Thermoelectric block body material.By test performance, its power factor in 723K is 564 μ Wm‐1K‐2, thermal conductivity
Rate is 0.77Wm‐1K‐1。
Embodiment 8：The addition of absolute ethyl alcohol is 10 times of block volume, dry powder by discharge plasma sintering into
Block materials, programming rate is 150 DEG C/min, and pressure is 60Mpa, soaking time 5 minutes, you can obtaining molecular formula is
BiAgSe0.97Te1.03Thermoelectric block body material.By test performance, its power factor in 723K is 596 μ Wm‐1K‐2, thermal conductivity
Rate is 0.71Wm‐1K‐1。
Embodiment 9：The addition of absolute ethyl alcohol is 10 times of block volume, dry powder by discharge plasma sintering into
Block materials, programming rate is 150 DEG C/min, and pressure is 60Mpa, soaking time 5 minutes, you can obtaining molecular formula is
BiAgSe0.96Te1.04Thermoelectric block body material.By test performance, its power factor in 723K is 618 μ Wm‐1K‐2, thermal conductivity
Rate is 0.87Wm‐1K‐1。
Embodiment 10：The addition of absolute ethyl alcohol is 10 times of block volume, dries powder by discharge plasma sintering
Into block materials, programming rate is 120 DEG C/min, and pressure is 60Mpa, soaking time 5 minutes, you can obtaining molecular formula is
BiAgSe0.95Te1.05Thermoelectric block body material.By test performance, its power factor in 723K is 626 μ Wm‐1K‐2, thermal conductivity
Rate is 0.94Wm‐1K‐1。
Embodiment 11：The addition of absolute ethyl alcohol is 10 times of block volume, dries powder by discharge plasma sintering
Into block materials, programming rate is 150 DEG C/min, and pressure is 50Mpa, soaking time 5 minutes, you can obtaining molecular formula is
BiAgSe1.01Te0.99Thermoelectric block body material.By test performance, its power factor in 723K is 425 μ Wm‐1K‐2, thermal conductivity
Rate is 0.74Wm‐1K‐1。
Embodiment 12：The addition of absolute ethyl alcohol is 10 times of block volume, dries powder by discharge plasma sintering
Into block materials, programming rate is 150 DEG C/min, and pressure is 50Mpa, soaking time 5 minutes, you can obtaining molecular formula is
BiAgSe1.02Te0.98Thermoelectric block body material.By test performance, its power factor in 723K is 405 μ Wm‐1K‐2, thermal conductivity
Rate is 0.76Wm‐1K‐1。
Embodiment 13：The addition of absolute ethyl alcohol is 10 times of block volume, dries powder by discharge plasma sintering
Into block materials, programming rate is 150 DEG C/min, and pressure is 50Mpa, soaking time 5 minutes, you can obtaining molecular formula is
BiAgSe1.03Te0.97Thermoelectric block body material.By test performance, its power factor in 723K is 435 μ Wm‐1K‐2, thermal conductivity
Rate is 0.77Wm‐1K‐1。
Embodiment 14：The addition of absolute ethyl alcohol is 10 times of block volume, dries powder by discharge plasma sintering
Into block materials, programming rate is 120 DEG C/min, and pressure is 60Mpa, soaking time 4 minutes, you can obtaining molecular formula is
BiAgSe1.04Te0.96Thermoelectric block body material.By test performance, its power factor in 723K is 415 μ Wm‐1K‐2, thermal conductivity
Rate is 0.70Wm‐1K‐1。
Embodiment 15：The addition of absolute ethyl alcohol is 10 times of block volume, dries powder by discharge plasma sintering
Into block materials, programming rate is 100 DEG C/min, and pressure is 60Mpa, soaking time 3 minutes, you can obtaining molecular formula is
BiAgSe1.05Te0.95Thermoelectric block body material.By test performance, its power factor in 723K is 403 μ Wm‐1K‐2, thermal conductivity
Rate is 0.68Wm‐1K‐1。
The BiAgSeTe base thermoelectricity materials that technical solution of the present invention is provided have relatively low thermal conductivity, electrical transmission higher
Characteristic, relatively current conventional alloys thermoelectric material has potential development trend, if will be big with reference to heavy metal element doping vario-property
Its thermoelectric transport properties is improved greatly, and BiAgSeTe sills are a kind of very potential new thermo-electric converting materials in a word.
Claims (2)
1. a kind of preparation method of BiAgSeTe base thermoelectricity materials, the chemical general formula of the BiAgSeTe base thermoelectricity materials is：
BiAgSe1-xTe1+x, the span of x is -0.05~0.05, it is characterised in that：With Bi, Ag, Se that purity is 99.99% and
Te simple substance powder is raw material, is weighed by the proportioning of chemical general formula, and grinding alms bowl with agate is well mixed raw material, is pressed into block and is put into
In vacuum drying chamber, drying temperature be 200 DEG C, process time is 48h, then by block Chan it is broken after be put into stainless steel jar mill,
Absolute ethyl alcohol wet-milling 12 hours under 400rpm are added, the addition of absolute ethyl alcohol is 5~10 times of block volume, then mill
Good powder is put into 60 DEG C of vacuum bellows and dries 24 hours, and dried powder is put into graphite jig, by discharge etc. from
Son sinters block materials into, and in sintering process, programming rate is 80 DEG C~150 DEG C/min, and sintering temperature is 450 DEG C, and pressure is
30Mpa~60Mpa, soaking time 3~6 minutes, you can obtain BiAgSeTe base thermoelectricity materials.
2. the preparation method of BiAgSeTe base thermoelectricity materials according to claim 1, it is characterised in that：The BiAgSeTe
X values in base thermoelectricity material chemical general formula are 0,0.002,0.004,0.008,0.01,0.02,0.03,0.04 or 0.05.
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Non-Patent Citations (2)
| Title |
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| Thermoelectric properties of Ag-doped n-type (Bi<sub>2</sub>Te<sub>3</sub>)<sub>0.9</sub>–(Bi<sub>2-x</sub>Ag<sub>x</sub>Se<sub>3</sub>)<sub>0.1</sub> (x=0-0.4) alloys prepared by spark plasma sintering;Cui J.L.,et al;《Journal of Solid State Chemistry》;20061215;第180卷(第3期);全文 * |
| Thermoelectric properties of p-type pseudo-binary (Ag<sub>0.365</sub>Sb<sub>0.558</sub>Te)<sub>x</sub>–(Bi<sub>0.5</sub>Sb<sub>1.5</sub>Te<sub>3</sub>)<sub>1-x</sub>(x=0-1.0) alloys prepared by spark plasma sintering;Cui J.L.,et al;《Journal of Solid State Chemistry》;20060817;第179卷(第12期);全文 * |
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